EP0604825B1 - Bei niedrigen Temperaturen flüssiges Urethan Prepolymer - Google Patents

Bei niedrigen Temperaturen flüssiges Urethan Prepolymer Download PDF

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Publication number
EP0604825B1
EP0604825B1 EP93120169A EP93120169A EP0604825B1 EP 0604825 B1 EP0604825 B1 EP 0604825B1 EP 93120169 A EP93120169 A EP 93120169A EP 93120169 A EP93120169 A EP 93120169A EP 0604825 B1 EP0604825 B1 EP 0604825B1
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EP
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Prior art keywords
glycol
isocyanate
urethane prepolymer
ether
polyol
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Expired - Lifetime
Application number
EP93120169A
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English (en)
French (fr)
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EP0604825A1 (de
Inventor
Haruo Watanabe
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Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4858—Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group

Definitions

  • This invention relates to a urethane prepolymer useful as a starting material of adhesives, coatings, synthetic leather, etc. More particularly, it relates to a urethane prepolymer which is liquid at low temperatures and thereby exhibits improved miscibility with a crosslinking agent, a filler for elastomer modification, a colorant, etc.
  • a polyurethane prepolymer is obtained by reacting a diol compound, such as a polyester glycol, a polyether glycol or a polycarbonate glycol, and an aliphatic or aromatic diisocyanate compound in the presence of excess isocyanate to form an isocyanate-terminated chain urethane compound.
  • a diol compound such as a polyester glycol, a polyether glycol or a polycarbonate glycol
  • the urethane prepolymer is further processed with various diol compounds or diamine compounds for chain extension or with a polyfunctional polyol for chain extension or curing in accordance with the end use to provide a urethane elastomer useful in the production of adhesives, coatings, synthetic leather, etc.
  • the urethane prepolymer is subjected to an addition reaction with a hydroxy allyl or acrylate compound, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or allyl alcohol, or an epoxy compound, such as glycidol or glycerol diglycidyl ether, to provide a urethane acrylate or a urethane epoxy resin useful in the production of adhesives or coatings.
  • a hydroxy allyl or acrylate compound such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or allyl alcohol
  • an epoxy compound such as glycidol or glycerol diglycidyl ether
  • Urethane prepolymers thus useful as an elastomeric material in various fields may have a wide variety of structures depending on the starting combination of a polyol and an isocyanate compound used for the preparation.
  • dihydroxypolyols selected from polytetramethylene ether glycol (PTG) obtained by ring-open polymerization of tetrahydrofuran, a polyol obtained by ring-open copolymerization of tetrahydrofuran and ⁇ -caprolactone, ⁇ -butyrolactone, ethylene oxide, propylene oxide, etc., and a polyether or polyether ester polyol obtained by block copolymerization of PTG and a glycol, e.g., polyethylene glycol, polypropylene glycol or polybutylene adipate, are widely employed because they provide urethane elastomers excellent in abrasion resistance, wet heat resistance, and impact resilience.
  • PTG polytetramethylene ether glycol
  • PTG and some of the copolymer polyols are capable of producing urethane prepolymers liquid at low temperatures.
  • urethane elastomers, urethane acrylates or urethane epoxy resins prepared from such low-temperature liquid urethane prepolymers have a short soft segment (i.e., short molecular chain length of the polyol) and therefore encounter difficulty in producing soft products, such as an elastomer, a coating film, or synthetic leather.
  • those prepolymers obtained from a dihydroxypolyol whose oxytetramethylene group has a molecular weight exceeding 600 tend to have a considerably increased viscosity or to crystallize in lower temperatures (10°C or lower). Therefore, they have poor miscibility with a chain extender, a crosslinking agent, a colorant, a plasticizer, or various fillers for elastomer modification, failing to provide a uniform compound.
  • a non-uniform prepolymer compound hardly produces an elastomer with excellent mechanical properties and also exhibits poor workability when used for the production of coatings or synthetic leather.
  • An object of the present invention is to provide a urethane prepolymer which does not crystallize in a temperature as low as 10°C or less.
  • a urethane prepolymer prepared by reacting a mixed polyol comprising a dihydroxypolyol selected from a polyether polyol or polyether ester polyol having an oxytetramethylene group and poly(tetramethylene ether/3-methyltetramethylene ether) glycol with an isocyanate compound.
  • the present invention provides an isocyanate-terminated urethane prepolymer prepared by a urethane reaction between (A) a dihydroxypolyol and (B) an isocyanate compound, wherein said dihydroxypolyol is a mixture of polyol (a) having a molecular weight of from 600 to 5000 and selected from a polyether ester glycol containing an oxytetramethylene group, a polytetramethylene ether glycol, or an oxytetramethylene group-containing glycol obtained by copolymerization of tetrahydrofuran with ethylene oxide or propylene oxide and having a molecular weight of from 600 to 5,000 and (b) poly(tetramethylene ether/3-methyltetramethylene ether) glycol comprising a structural unit represented by formula (I): -CH 2 CH 2 CH 2 CH 2 O- and from 5 to 40% by weight of a structural unit represented by formula (II) based on polyol (b):
  • the Polyol (a) i.e., a polyether glycol containing an oxytetramethylene group or a polyether ester glycol containing an oxytetramethylene group to be contained in dihydroxypolyol 1 (A), comprises PTG obtained from ring-open polymerization of tetrahydrofuran, oxytetramethylene group-containing glycols obtained by copolymerization of tetrahydrofuran and ⁇ -caprolactone, ⁇ -butyrolactone, ethylene oxide or propylene oxide as disclosed in JP-A-63-105030 and JP-A-63-178131 (the term "JP-A" as used herein means an "unexamined published Japanese patent application”), and oxytetramethylene group-containing polyols obtained by block copolymerization of oxytetramethylene glycol and a glycol compound, e.g., polyethylene adipate, polypropylene adipate or polybuty
  • the molecular weight of the polyols in the present invention means a number average molecular weight, and can be obtained, for example, by measuring the number of the hydroxyl groups present in the polyols by means of the acetylation method.
  • Polyol (b) which is used in the present invention serves as a crystallization inhibitor at a low temperature, and consists of (I) and (II) as structural units.
  • the mode of polymerization of structural units (I) and (II) is random copolymerization.
  • Polyol (b) is obtained by random copolymerization of tetrahydrofuran and 3-methyltetrahydrofuran in the presence of a known polymerization initiator either alone or in combination with an anhydride or an accelerator.
  • Usable polymerization initiators include protonic acids, e.g., HClO 4 , HSO 3 F, HSO 3 Cl, and HBF 4 ; ion complexes, e.g., (C 2 H 5 ) 3 OBF 3 , CH 3 COSbCl 6 , and C 6 H 5 N 2 PF 6 ; and catalyst systems for ring-open polymerization of tetrahydrofuran, e.g., CH 3 COCl-BF 3 , SOCl 2 -AlCl 3 , and POCl 3 -FeCl 3 .
  • protonic acids e.g., HClO 4 , HSO 3 F, HSO 3 Cl, and HBF 4
  • ion complexes e.g., (C 2 H 5 ) 3 OBF 3 , CH 3 COSbCl 6 , and C 6 H 5 N 2 PF 6
  • catalyst systems for ring-open polymerization of tetrahydrofuran
  • the content of structural unit (II) in polyol (b) is from 5 to 40% by weight, and more preferably from 8 to 25% by weight.
  • Polyol (b) has a molecular weight of from 500 to 5,000, and preferably from 800 to 3,000.
  • the mixing ratio of polyol (b) in total dihydroxypolyol (A) is in the range of from 1 to 50% by weight, and preferably from 3 to 30% by weight.
  • Isocyanate compound (B) which can be used in the present invention includes 4,4'-diphenylmethane diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 1,4-hexylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, and tetramethylxylene diisocyanate.
  • Carbodiimide-modified diisocyanate compounds such as carbodiimide-modified 4,4'-diphenylmethane diisocyanate, may also be used.
  • the urethane prepolymer according to the present invention can be prepared by reacting dihydroxypolyol (A) with diisocyanate compound (B) at a B/A molar ratio of from 1.2 to 2.2, and preferably from 1.5 to 2.0.
  • the reaction is carried out with stirring at a temperature of from 40° to 120°C, and preferably from 60° to 90°C, for a period of from 2 to 5 hours.
  • a mixed polyol consisting of 90.0 g of PTG-850SN and 10 g of poly(tetramethylene ether/3-methyltetramethylene ether) glycol (3-methyltetramethylene ether unit content: 16%; molecular weight: 1,000) and 30.8 g of 2,4-tolylene diisocyanate were reacted in the same manner as in Example 1 to obtain an isocyanate-terminated urethane prepolymer (isocyanate/polyol molar ratio: 1.5).
  • a mixed polyol consisting of 95.0 g of PTG-850SN and 5.0 g of poly(tetramethylene ether/3-methyltetramethylene ether) glycol (3-methyltetramethylene ether unit content: 16%; molecular weight: 1,000) and 31.0 g of 2,4-tolylene diisocyanate were reacted in the same manner as in Example 1 to obtain an isocyanate-terminated urethane prepolymer (isocyanate/polyol molar ratio: 1.5).
  • a mixed polyol consisting of 108.0 g of PTG-1000 and 12.0 g of poly(tetramethylene ether/3-methyltetramethylene ether) glycol (3-methyltetramethylene ether unit content: 16%; molecular weight: 1,000) and 33.9 g of 2,4-tolylene diisocyanate were reacted in the same manner as in Example 1 to obtain an isocyanate-terminated urethane prepolymer (isocyanate/polyol molar ratio: 1.6).
  • a mixed polyol consisting of 97.0 g of PTG-1000 and 3.0 g of poly(tetramethylene ether/3-methyltetramethylene ether) glycol (3-methyltetramethylene ether unit content: 16%; molecular weight: 1,000) and 34.7 g of 2,4-tolylene diisocyanate were reacted in the same manner as in Example 1 to obtain an isocyanate-terminated urethane prepolymer (isocyanate/polyol molar ratio: 2.0).
  • Polytetramethylene ether glycol (“PTG-2000" produced by Hodogaya Chemical Co., Ltd.; molecular weight: 2,070) was mixed with poly(tetramethylene ether/3-methyltetramethylene ether) glycol (3-methyltetramethylene ether unit content: 16%; molecular weight: 1,990) to prepare a mixed polyol having the content of the latter polyol of 50%, 30% or 10%.
  • An isocyanate-terminated urethane prepolymer having an isocyanate/polyol molar content of 2.0 was prepared from each of the mixed polyols and 2,4-tolylene diisocyanate in the same manner as in Example 1.
  • a mixed polyol consisting of 97.0 g of PTG-2000 (molecular weight: 2,070) and 3.0 g of poly(tetramethylene ether/3-methyltetramethylene ether) glycol (3-methyltetramethylene ether unit content: 16%; molecular weight: 1,990) and 16.9 g of 2,4-tolylene diisocyanate were reacted in the same manner as in Example 1 to obtain an isocyanate-terminated urethane prepolymer (isocyanate/polyol molar ratio: 2.0).
  • An isocyanate-terminated urethane prepolymer was prepared in the same manner as in Comparative Example 1, except for changing the isocyanate/polyol molar ratio to 2.0.
  • the urethane prepolymer according to the present invention exhibits liquid nature at low temperature of 10°C or even less and therefore shows improved workability on mixing with a chain extender, a crosslinking agent, an elastomer modifying filler, and so forth.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (5)

  1. Mit Isocyanat abgeschlossenes Urethanprepolymer, das hergestellt wurde durch eine Urethanreaktion zwischen (A) einem Dihydroxypolyol und (B) einer Isocyanatverbindung, wobei besagtes Dihydroxypolyol eine Mischung von Polyol (a), welches ein Molekulargewicht von 600 bis 5000 hat und ausgewählt ist aus einem Polyetheresterglykol, welches eine Oxytetramethylengruppe enthält, einem Polytetramethylenetherglykol oder einem Oxytetramethylengruppehaltigen Glykol, welches durch Copolymerisation von Tetrahydrofuran mit Ethylenoxid oder Propylenoxid erhalten wird und von (b) Poly(tetramethylenether/3-methyltetramethylenether)glykol ist, welches eine Struktureinheit, die durch die Formel (I) dargestellt wird: -CH2CH2CH2CH2O- und von 5 bis 40 Gew.% einer Struktureinheit umfaßt, die durch die Formel (II) basierend auf (b) Poly(tetramethylenether/3-methyltetramethylenether)glykol dargestellt wird:
    Figure 00180001
    in der R1 und R2 jeweils ein Wasserstoffatom oder eine Methylgruppe umfassen, wobei wenigstens eine von ihnen eine Methylgruppe ist, und das ein Molekulargewicht von 500 bis 5.000 hat, wobei der Anteil von (b), welcher auf dem Gesamtgehalt von Dihydroxypolyol (A) basiert, von 1 bis 50 Gew.% ist, bei einem B/A molaren Verhältnis von 1,2 bis 2,2.
  2. Mit Isocyanat abgeschlossenes Urethanprepolymer nach Anspruch 1, dadurch gekennzeichnet, daß besagtes Polyetherglykol oder Polyetheresterglykol, das eine Oxytetramethylengruppe enthält, ein Molekulargewicht von 800 bis 2.000 hat.
  3. Mit Isocyanat abgeschlossenes Urethanprepolymer nach Anspruch 1, dadurch gekennzeichnet, daß besagtes Poly(tetramethylenether/3-methyltetramethylenether)glykol (b) von 8 bis 25 Gew.% besagter Struktureinheit (II) umfaßt.
  4. Mit Isocyanat abgeschlossenes Urethanprepolymer nach Anspruch 1, dadurch gekennzeichnet, daß besagtes Poly(tetramethylenether/3-methyltetramethylenether)glykol (b) ein Molekulargewicht von 800 bis 3.000 hat.
  5. Mit Isocyanat abgeschlossenes Urethanprepolymer nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil von besagtem Poly(tetramethylenether/3-methyltetramethylenether)glykol (b), basierend auf dem Gesamtgehalt von Dihydroxypolyol (A), von 3 bis 30 Gew.% ist.
EP93120169A 1992-12-22 1993-12-14 Bei niedrigen Temperaturen flüssiges Urethan Prepolymer Expired - Lifetime EP0604825B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP356456/92 1992-12-22
JP35645692 1992-12-22

Publications (2)

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EP0604825A1 EP0604825A1 (de) 1994-07-06
EP0604825B1 true EP0604825B1 (de) 1998-08-26

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EP (1) EP0604825B1 (de)
KR (1) KR940014488A (de)
DE (1) DE69320610T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10151709B4 (de) * 2000-10-19 2007-08-02 Dainippon Ink & Chemicals, Inc. Verfahren zur Herstellung eines flüssigen Urethan-Prepolymeren und Harzmasse

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI705081B (zh) 2019-08-20 2020-09-21 南亞塑膠工業股份有限公司 用於製作塑膠跑道的聚氨酯接著劑及其預浸體

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JPH07116276B2 (ja) * 1987-03-25 1995-12-13 保土谷化学工業株式会社 ポリウレタン樹脂の製造方法
JP2627626B2 (ja) * 1987-10-20 1997-07-09 日本合成ゴム株式会社 光フアイバー被覆用組成物
US5000899A (en) * 1988-05-26 1991-03-19 E. I. Du Pont De Nemours And Company Spandex fiber with copolymer soft segment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10151709B4 (de) * 2000-10-19 2007-08-02 Dainippon Ink & Chemicals, Inc. Verfahren zur Herstellung eines flüssigen Urethan-Prepolymeren und Harzmasse

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US5354837A (en) 1994-10-11
EP0604825A1 (de) 1994-07-06
KR940014488A (ko) 1994-07-18
DE69320610T2 (de) 1999-02-11
DE69320610D1 (de) 1998-10-01

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